EP3594313A1 - Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions - Google Patents

Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions Download PDF

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Publication number: EP3594313A1
Authority: EP; European Patent Office
Prior art keywords: process stage; energy; gas; pyrolysis; pressure
Prior art date: 2009-11-20
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP19190005.9A

Other languages

German (de)

English (en)

Inventor

Mikael Rüdlinger

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Rv Lizenz AG

Original Assignee

Rv Lizenz AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2009-11-20

Filing date

2010-11-19

Publication date

2020-01-15

2009-11-20 Priority claimed from EP09176684A external-priority patent/EP2325288A1/fr

2010-01-22 Priority claimed from EP10151481.8A external-priority patent/EP2348254B1/fr

2010-01-22 Priority claimed from EP10151473A external-priority patent/EP2348253A1/fr

2010-11-19 Application filed by Rv Lizenz AG filed Critical Rv Lizenz AG

2020-01-15 Publication of EP3594313A1 publication Critical patent/EP3594313A1/fr

Status Withdrawn legal-status Critical Current

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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C—CHEMISTRY; METALLURGY
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C—CHEMISTRY; METALLURGY
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
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- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
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- F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
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- F02C3/26—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension
- F02C3/28—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
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- C10G2300/4037—In-situ processes
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- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

the invention relates to methods and devices for emission-free energy production by thermal chemical processing and recycling of solid, liquid and gaseous carbonaceous materials and mixtures, in particular waste, biomass, coal, and other heterogeneous materials.
the invention further relates to devices for generating electrical and mechanical energy and corresponding methods, and also to the production of synthetic hydrocarbons, and their use in such devices.
carbon dioxide is an inevitable by-product of energy generation. With reasonable energy and / or economic effort, it is generally not possible to separate carbon dioxide from the combustion gases that are produced.
gas mixtures can be produced from solid, liquid and gaseous carbon-containing materials, which are then used as so-called synthesis gas for chemical syntheses.
Synthesis gases with carbon monoxide and hydrogen are used, for example, for industrial liquid-phase methanol synthesis or for Fischer-Tropsch synthesis for the production of hydrocarbons and other organic materials.
synthesis gases are also used to generate energy, for example as a fuel for operating heat engines.
the thermal energy required for the endothermic reactions I and II to proceed can, for example, come from partial combustion of the solid carbon in reaction III, or be supplied externally.
the solid carbon for the gasification reactions is in the form of coke. This is in turn generated in a previous process step by pyrolysis of coal or other carbon-containing materials.
the pyrolysis gases produced during the pyrolysis are burned, the hot carbon dioxide-containing combustion gases serving both as a gasifying agent for the coke and as an external heat energy supplier.
the coke is gasified with the addition of air / oxygen, the thermal energy being generated primarily by the partial combustion of the carbon of the coke.
Pyrolysis gas from a previous pyrolysis stage is then mixed into the hot synthesis gas, where it is cracked, so that a tar-free combustible gas mixture is formed.
a disadvantage of the known methods is the generation of emissions, the low efficiency, and the complicated structure and operation, particularly in plants in which coke is gasified in the eddy current or entrained flow.
the pyrolysis coke is ground and blown into the gas stream of the second process stage, where the coke dust is gasified endothermically in the entrained flow to synthesis gas.
a corresponding procedure is described in EP 1749872 A2 disclosed.
the resulting synthesis gas is used to produce diesel-analog fuel in a multi-stage Fischer-Tropsch synthesis. Resulting exhaust gases including the carbon dioxide generated in the pyrolysis and gasification stage are released into the atmosphere.
exhaust gases consisting mainly of carbon dioxide and possibly inert gases such as air-nitrogen are released into the atmosphere.
the object of the invention is to provide methods and devices for emission-free energy generation by thermal-chemical processing and recycling of solid, liquid and gaseous carbonaceous materials and mixtures, in particular waste, biomass, coal and other heterogeneous materials, which the above mentioned and do not have other disadvantages.
Methods and devices according to the invention should in particular be as emission-free as possible.
Another object of the invention is to provide methods and devices with which solid, liquid or gaseous materials can be efficiently converted into gaseous or liquid energy sources.
Such a device according to the invention for emission-free energy generation should advantageously store part of the generated energy and, if the power requirement is increased, be able to release this stored energy again as chemical and / or electrical and / or mechanical and / or thermal energy.
Another object of the invention is to provide a device for emission-free energy generation that is independent of external conditions such as pressure, temperature, humidity or other external parameters. For example, in higher locations, the lower ambient pressure has a negative impact on the performance of conventional power plants.
the gas flow within the circuit advantageously runs in a certain direction.
the gas stream can flow, for example, within the cycle from the first process stage via the second process stage to the third process stage and again to the first process stage, or from the first process stage via the third process stage to the second process stage and back to the first process stage.
the first process stage of the recycling process can be carried out in one or more pressure reactors.
the first process stage is advantageously carried out at a temperature between 300 and 800 ° C., preferably between 450 and 700 ° C., and particularly preferably between 500 and 600 ° C.
the second process stage of the recovery process can also be carried out in one or more second pressure reactors.
Oxygen and / or water vapor and / or carbon dioxide can be used as the gasification agent for the gasification reaction in the second process stage.
the second process stage of the recycling process according to the invention is advantageously carried out at a temperature between 600 and 1600 ° C., preferably between 700 and 1400 ° C., and particularly preferably between 850 and 1000 ° C.
the third process stage of the recycling process is advantageously carried out in one or more pressure reactors.
the conversion in the third process stage is preferably carried out using a Fischer-Tropsch synthesis or a liquid-phase methanol synthesis.
electrical and / or mechanical energy is generated by oxidation of the hydrocarbons and / or other solid, liquid and / or gaseous products of the third process stage to an oxidation gas consisting essentially of carbon dioxide and water.
an oxidation gas consisting essentially of carbon dioxide and water.
Pure oxygen is advantageously used as the oxidizing agent.
Water can be condensed out and / or separated from the oxidation gases.
At least some of the oxidation gases of the drive device are fed back into the first process stage and / or the second process stage and / or the third process stage of the method.
the synthesis gas is cooled in a heat exchanger, water vapor and / or another hot gas being produced, from which electrical and / or mechanical energy is generated using a heat engine, preferably a steam turbine.
a transport line for the pyrolysis gas connects the first subunit pressure-tightly to the second subunit and / or to the third subunit.
a transport line for the synthesis gas connects the second subunit pressure-tightly to the third subunit and / or to the first subunit.
a transport line for the return gas connects the third subunit pressure-tightly to the first subunit and / or to the second subunit.
At least one compressor is advantageously arranged along at least one of the transport lines of the processing unit.
Means can be provided which allow a gas flow to flow along the transport lines only in a certain direction, preferably from the first subunit via the second subunit to the third subunit and again to the first subunit, or from the first subunit via the third subunit to the second subunit and back to the first subunit.
the subunits of the utilization unit can each have one or more pressure reactors.
the first and / or the second subunit have heating devices and / or heat exchangers.
a branching of the transport line of the synthesis gas can be provided, with which a part of the synthesis gas can be returned from the second subunit to the first pressure reactor.
the first subunit and the second subunit of the utilization unit have a common pressure reactor.
the third subunit of the utilization unit preferably comprises a Fischer-Tropsch synthesis stage or a liquid-phase methanol synthesis stage, or another suitable stage for the production of solid, liquid or gaseous products.
a recycling system that can be operated in such a way that there is a pressure drop from the first subunit via the second subunit to the third subunit is particularly advantageous. In this way, the mass is transported along the cyclic gas flow, driven by the pressure difference between the different pressure reactors. This is a major advantage, because it means that the system needs as few moving components as possible.
a particular advantage of the invention is that the device is independent of external conditions such as pressure, temperature, humidity or all other external parameters. Since the material flow is closed in the devices according to the invention, the method is essentially independent of the ambient pressure.
Another important advantage of a device according to the invention is that the closed system does not require gas treatment. Another advantage is that the formation and separation of liquid products from the synthesis gases in the third process stage inevitably leads to the separation of particles.
a particularly advantageous embodiment of a device according to the invention comprises an energy system which is set up to generate electrical and / or mechanical and / or thermal energy as operating materials using hydrocarbons and / or other products from the recycling system.
a drive device for generating electrical and / or mechanical energy from the operating materials is advantageously provided in the energy system, said drive device receiving the energy required for operation from the oxidation of the operating materials to an oxidizing gas consisting essentially of carbon dioxide and water, and a device for compression and / or condensation of the oxidizing gas.
the drive device can be configured as a fuel cell or as a heat engine.
the drive device can be operated with pure oxygen as the oxidizing agent.
a heat exchanger for cooling the oxidizing gas stream is provided before and / or after the device for compressing and / or condensing the oxidizing gas.
a device for condensing and / or separating water from the oxidizing gas is provided. Among other things, this reduces the amount of residual gas remaining.
Another variant of a device according to the invention comprises a memory for collecting the oxidizing gas or residual gas after compression and / or condensation of the oxidizing gas.
a transport line can be provided for returning the oxidation gases or residual gases to one of the three process stages of the recycling plant of a device according to the invention.
the drive device of the energy system is designed as an internal combustion engine, with at least one combustion chamber for the combustion of liquid or gaseous fuel with oxygen, with means for converting the gas pressure or gas volume into mechanical work, with a feed device for introducing oxygen into the combustion chamber, and with a ventilation device for removing the oxidizing gases from the combustion chamber.
a supply device for introducing water and / or water vapor into the combustion chamber and / or into the oxidizing gas stream after the outlet from the combustion chamber is provided in the drive device of the energy system.
the drive device can comprise, for example, a turbine device which is operated with the oxidizing gas stream.
the recycling system comprises an energy unit for generating electrical and / or mechanical energy, with at least one drive device for generating electrical and / or mechanical energy from water vapor and / or other hot gases which are used in the recycling unit of the Recovery facility generated and / or overheated.
the energy unit of the recycling system has a drive device for generating electrical and / or mechanical energy from water vapor or other hot gases, which was generated and / or overheated in the recycling unit are.
At least one heat exchanger is provided in the circuit of the recycling unit for heating water vapor and / or other gases and / or for generating water vapor.
Another particularly advantageous device comprises a plant for producing hydrogen and means for supplying the hydrogen to the recovery unit.
Hydrocarbons and other solid, liquid and / or gaseous products which have been produced using a method according to the invention or with a device according to the invention can be distinguished from analog petroleum products, for example by the absence of typical sulfur and phosphorus impurities.
Such products When manufactured with portions of the starting material from biomass, such products have increased C14 isotope portions compared to petrochemical products.
Figure 1 shows schematically a possible embodiment of a device Z according to the invention for the emission-free generation of energy and / or hydrocarbons and other products by recycling carbon-containing materials, with a system A for the thermal-chemical recycling of carbon-containing materials M10 to hydrocarbons and other products M60 and / or liquid and / or gaseous operating materials M61 (chemical energy), and for the generation of electrical and / or mechanical energy E1.
the recycling plant A comprises a loading unit AH, in which the still unprocessed carbon-containing raw material M10 to be recycled is processed into carbon-containing raw material M11.
residues M17 may arise that may be reusable, e.g. Metals.
the centerpiece of the recycling plant A is the recycling unit AB, in which the processed carbon-containing materials M11 are fed and pyrolysed in a first subunit AC to a first process stage P1, pyrolysis coke M21 and pyrolysis gas M22 being produced.
a second subunit AD of a second process stage P2 the pyrolysis coke M21 is gasified from the first process stage, synthesis gas M24 being produced and slag and other residues M90 remaining.
a third subunit AE of a third process stage P3 the synthesis gas M24 from the second process stage is converted into hydrocarbon-based solid, liquid and / or gaseous products M60, M61. All three process stages are closed pressure-tight and form an essentially closed circuit.
Thermal energy generated in a recycling method according to the invention can be removed in the form of steam M52 from the recycling unit AB and used in an energy unit AF to generate electrical and / or mechanical energy E1 by means of a suitable drive device such as a steam turbine (not shown). Heating compressible media, such as nitrogen, for operating the drive device is also possible and advantageous. A certain basic service can thus be generated during a constant operation of the utilization unit AB.
the energy unit AF is an optional component of a device according to the invention.
a discharge unit AG is used to discharge and process the ash and other solid residues M90.
the device according to the invention can also have an energy system C, for the emission-free generation of electrical and / or mechanical energy E2, or thermal energy E4, by utilizing the carbon-containing products M61 from the utilization system A as operating materials. Resulting oxidation gases M27 are returned to treatment plant A so that no emissions arise.
the energy system C can be designed, for example, as a heating system for generating thermal energy E4 for heating buildings.
the energy system can also be designed as an electrical power plant for generating electrical energy E2.
a plant B is advantageously switched on for the transport and the intermediate storage of the operating materials and oxidizing gases.
a system B can also contain means for processing the operating materials M61 for use in the energy system C.
the hydrocarbon-containing operating materials M61 generated in the synthesis process stage P3 are stored temporarily, in tanks or pressure reservoirs of system B (not shown).
the operating materials M61 are removed from these stores as required and converted into electrical and / or mechanical energy E2 in the energy system C using a suitable drive device. This can be done for example by means of a heat engine or a fuel cell device. Residual gas M26 containing carbon dioxide from the energy system C is returned to the recycling unit AB. If necessary, a buffer can be provided again.
the energy system C offers the advantage that the energy output produced by the device Z according to the invention can be adapted in a very short time to the currently required requirement.
the chemical operating fluids M61 serve as temporary energy storage.
a suitably designed drive device for example a gas turbine and / or steam turbine operated with the operating materials M61, can be put into operation very quickly and generate electrical and / or mechanical energy.
the peak power of the device Z can briefly exceed the basic thermal power of the device Z due to the energy storage capacity of the chemical operating materials M61.
the energy plant C can be installed together with the recycling plant A at the same location.
the energy system C is arranged spatially separated from the recycling system A.
the operating materials M61 and the oxidation gases M27 can be transported, for example, by rail, ship or pipeline, in which case the transport device (tanker, tank on ship, pipeline) also serves as a buffer BA, BB.
the overall system of material transport between plants A and C is to be regarded as part of plant B for the transport and temporary storage of the operating materials and oxidizing gases.
the location of the peak load energy system can be C of a device Z according to the invention can be selected where the corresponding need arises, while the recycling plant A is advantageously set up where the carbon-containing starting materials M10 are obtained.
a device according to the invention can furthermore have a system D for the production and supply of external chemical energy.
a system D for the production and supply of external chemical energy For example, hydrogen M32 can be produced and supplied as a source of external chemical energy.
FIG Figure 3 A possible embodiment of a recycling plant A of a device Z according to the invention is shown in FIG Figure 3 shown schematically.
the system A shown comprises a recycling unit AB for recycling the carbon-containing starting material M11, and an energy unit AF for generating an essentially constant basic quantity E1 of electrical and / or mechanical energy.
the structure of the recycling unit AB essentially corresponds to the exemplary recycling unit that will be described later with the aid of Figure 9 will be discussed.
the base load energy unit AF is only shown as a block. A possible embodiment is in Figure 3A be discussed.
superheated steam M52 is generated from colder steam M51 (approx. 550-600 ° C / 50 bar). If necessary, a subsequent further heat exchanger can cool the synthesis gas stream further.
the superheated steam M52 is fed into the energy unit AF, where it is used for electrical and / or mechanical energy E1.
the remaining steam condensate M41 is returned to the processing unit AB, where it is converted into steam M51 in the third process stage P3, and this steam M51 is then converted again into superheated steam M52 in the heat exchanger / superheater A44.
the exemplary embodiment of the energy unit AF in Figure 3A comprises a drive device A61 in the form of a steam turbine A62 or another heat engine which can be operated with superheated steam M52 for generating mechanical energy, and in the example shown a generator device A64 which is driven by the steam turbine and which generates electrical energy E1.
the exhaust steam M53 is condensed in the condenser / economizer A63, the waste heat being removed via a suitably designed cooling circuit A65.
the resulting condensate M41 is preferably 60-70 ° C hot, so that the water in the subsequent boiler stage A32 of the treatment plant AB does not have to be heated too much. At the same time, the water should not be too hot to avoid cavitation in the A66 pump.
the condensate M41 is pumped with the pump A66 from an intermediate store (not shown) into the heat exchanger / boiler A32 of process stage P3, where it is evaporated again to steam M51 (approx. 250-300 ° C / 20 bar), with simultaneous cooling synthesis stage P3.
the steam M51 is stored in a steam dome (not shown), on the one hand to separate water remaining before entering the superheater A44, and on the other hand to form a store from which the process steam M50 can be removed for the various purposes in the processing unit AB , Losses in the circuit and consumption of process steam M50 are compensated for by supplying water to the condensate store (not shown).
part of the steam can be removed as process steam M50 in the steam turbine A62 after the high pressure stage, which is shown in Figure 3A shown as a dashed arrow is.
process steam M50 in the steam turbine A62 after the high pressure stage, which is shown in Figure 3A shown as a dashed arrow is.
the exhaust steam from process steam consumers such as the heat exchangers A45, A17 can also be condensed M41 and returned to the feed water M40, so that the energy cycle is as closed as possible.
the water vapor cycles can also be guided differently through the various heat exchangers in order to achieve the highest possible efficiency in plant A.
the products produced in synthesis stage P3 can be used as operating material M61 for a conventional fossil fuel energy system C, for example diesel generators or gas turbine generators, which can be used to cover peak loads.
the chemical operating fluids M61 serve to achieve very high production outputs for a short time, detached from the basic system AB, AF, which is in an equilibrium state.
the total output of the device Z can be increased from, for example, 100% constant base load production P c2 to, for example, 600% peak load production P e2 within a very short period of time.
the M60 products can also be used for other purposes, for example for the production of fuels or as educts for the chemical industry.
Such a device according to the invention has the advantage over conventional systems, among other things, that in the recycling unit AB, because of the closed material flow within the three-stage process, there is no need for flue gas filters and catalyst devices for cleaning the combustion exhaust gases. This leads to a reduction in the number of components of such a system, and thus to lower investment costs and operating costs.
such a recycling unit also requires less space, since no filter systems, chimneys, etc. are required, and the volume of the material flows is lower due to the high pressure.
an energy system C operated with operating materials M61 from the recycling plant A is provided to cover peak loads E2.
the energy system C is designed in such a way that the carbon dioxide produced during energy generation is fed back into the cycle of the recycling system A, so that no emissions arise.
the operating materials M61 are advantageously obtained from an intermediate storage BA of the transport / storage system B, for example a tank system or a pressure accumulator, in order to bridge peak demand.
an intermediate storage BA of the transport / storage system B for example a tank system or a pressure accumulator
the resulting carbon dioxide-containing residual gases M26 from the energy system B can be collected in a buffer store BB and stored.
a possible embodiment of an energy unit C is shown in FIG Figure 4A shown.
a drive device C11 generates electrical and / or mechanical energy E2 by means of chemical energy carriers M61 from the synthesis stage P3 of the utilization unit AB.
Said drive device C11 can be, for example, a heat engine in which the heat generated when the operating materials M61 are oxidized to carbon dioxide is converted into mechanical work, for example for operating a generator system (not shown), or a fuel cell system in which the oxidation reaction is carried out directly Power generation E2 is used.
Such a drive device C11 has a closed circuit, that is to say it does not cause any emissions to the atmosphere.
the oxidation gases M27 that occur during the performance of the mechanical work, which essentially only contain carbon dioxide and possibly also water, are post-treated C12, compressed C13, and the remaining residual gas M26 is fed back into the circuit of the recycling plant AB.
a buffer BB is provided, as in Figure 4 shown.
the system C of the device Z according to the invention can be arranged separately from the recycling system A.
the thermal or electrical energy-generating oxidation reaction takes place in the drive device C11 with pure oxygen M31 instead of with air.
oxygen M31 instead of air avoids the formation of nitrogen oxides on the one hand due to the absence of atmospheric nitrogen in a thermal-chemical reaction at high temperatures, but above all only carbon dioxide and water vapor remain in the resulting oxidation gases M27.
the resulting gases can also contain certain proportions of carbon monoxide and unreacted fuel. These can also be fed into the recycling system A without problems.
the reaction products M27 of the energy-generating oxidation reaction are essentially gaseous.
the corresponding oxidizing gas mixture is now compressed C13 to reduce the volume.
the oxidizing gas mixture M27 can be cooled before and / or after compression.
Water M41 is condensed out and separated, leaving only carbon dioxide in the residual gas M26, possibly with proportions of carbon monoxide and unreacted fuel.
the residual gas M26 is now fed to the first process stage P1 of the recycling unit AB of plant A, so that a closed material cycle results.
the residual gas M26 can also be led into the second process stage P2 or the third process stage P3, which is shown in Figure 4 is indicated by dashed arrows.
liquid or gaseous hydrocarbons and hydrocarbon derivatives can be produced from carbon-containing materials M11 in a device Z according to the invention, and the resulting high-quality operating medium mixture M61 is subsequently converted into electrical energy E2.
the carbon dioxide produced is recycled and partially or completely converted back into fuel M61 in recycling plant A. In this way, the effective carbon dioxide emissions of the peak load generator system C can be greatly reduced or even avoided altogether.
the drive device can also be operated without problems in combination operation with hydrogen M32 as a further operating material.
the hydrogen content leads to a reduction in the accumulated residual gas quantity M26 after the heat exchanger / condenser and compressor, since only water is produced when hydrogen is oxidized with oxygen.
FIG Figure 5 Another advantageous embodiment of a device Z according to the invention is shown in FIG Figure 5 shown.
this includes both a base load energy unit AF and a peak load energy system C.
a recycling method according to the invention chemical energy in the form of molecular hydrogen is introduced into the method in larger quantities.
a device Z according to the invention is, for example, in FIG Figure 6 (a) shown schematically.
the recycling plant A picks up matter in the form of carbon-containing starting materials M10, as have already been discussed above.
Carbon dioxide M33 is also suitable as a carbon source.
the primary source of energy is the chemical energy of the molecular hydrogen M32.
hydrogen serves to reduce the starting materials, and on the other hand, oxidation with oxygen leads to the supply of thermal energy.
Molecular hydrogen M32 can be produced from water by electrolysis, which also produces molecular oxygen M31. Electrical energy E3 can be converted into chemical energy in this way.
the gaseous molecular hydrogen has a significantly lower energy density compared to liquid fuels, but also compared to gaseous hydrocarbons, which means that it has so far not been able to establish itself as a fuel for vehicles.
the chemical energy of hydrogen can be efficiently converted into chemical energy in the form of high-quality hydrocarbons and other products.
the oxygen M31 obtained during the electrolysis is also advantageously used to introduce the entire chemical energy into the process, or a maximum of the electrical energy inserted into the electrolysis.
a system D provides molecular hydrogen M32 and oxygen M31.
the electrical energy E3 for the electrolysis reaction preferably comes from regenerative energy sources (wind power, solar energy, water energy, etc.).
This has the great advantage that an inherent disadvantage of wind turbines DA and solar energy systems DB can be overcome, namely the cyclical energy production, which cannot always be guaranteed due to the dependence on external factors. This leads to correspondingly low achievable market prices for the electrical energy generated.
the hydrogen, and if possible also the oxygen, is then used in a process according to the invention, for example in order to produce easier-to-handle liquid operating materials with a higher energy density, or other high-quality products.
the energy of the energy generation units DA, DB of the system D is transported as electrical current E3 to the electrolysis unit DC, which is located at the location of the recycling system A and in which hydrogen M32 and oxygen M31 are generated locally. Part of the oxygen is not required and can be used for other purposes, for example in an energy system C of the invention Device Z.
Intermediate storage units DE, DF for example in the form of pressure tanks, serve as buffers to compensate for the fluctuating energy production of the energy generation units DA, DB.
the recycling plant A produces high-quality hydrocarbons and other synthesis products M60, as well as energy E1 if necessary, residues M90 are continuously removed from the system.
Water can also be easily removed from the system, for example by condensation M41.
water serves primarily as an oxidizing and gasifying agent if no oxygen is available.
water removed from the system M41 also serves as a sink for oxygen. This is particularly relevant if the system absorbs large amounts of M33 carbon dioxide as a carbon source.
a recycling process according to the invention can also produce high-quality and high-energy hydrocarbon products M60 from comparatively low-energy carbon sources.
the method can in principle only be carried out using pure carbon dioxide as the carbon source. Since the supplied electrical energy comes directly or indirectly (wind power, hydropower) from the sun, this results - from a fundamental point of view - as it were an artificial photosynthesis, namely the generation of carbon compounds from carbon dioxide, water and sunlight.
the combination of the recycling plant A with an energy plant C is optional.
FIGS Figures 7 (a) to (d) The difference in the performance spectrum of a device Z according to the invention in comparison with a conventional power plant operated with carbon-containing operating materials is shown in FIGS Figures 7 (a) to (d) explained in more detail.
Figure 7 (a) shows schematically the performance profile of a conventional thermal power plant.
the vertical axis represents the power P and the horizontal axis the time t.
the power plant has an added heat content P a , that is, the thermal energy or power contained in the fuel as chemical energy, and an effective thermal power P b , that is, the thermal energy per unit of time that can be effectively converted into electrical or mechanical energy.
P a the thermal energy or power contained in the fuel as chemical energy
P b effective thermal power
the electrical power requirement P e in a conventional power grid varies both during the day and during the week.
the total nominal power of such a power plant must be aligned to the peak load. This means that the dimensioning of the system is larger because of the peak power required than would actually be necessary due to the average total power.
Such a device Z converts a constant part of the chemical energy supplied in the form of the carbonaceous materials M10, M11 into thermal energy in the form of water vapor, which is then converted into electrical energy P f , for example with a steam turbine of the base load energy unit AF ,
a further portion of the chemical energy supplied in the form of the carbon-containing materials M10, M11 is converted in the synthesis stage P3 of the utilization unit AB with a constant production output P g into chemical energy in the form of high-quality carbon-containing operating materials M61, for example diesel-like products or gaseous products such as propane.
These operating materials can be stored in any quantity BA and / or as in Figure 2 executed over short or long distances.
Figure 7 (d) shows schematically the profile of the total power P e of a device according to the invention over the course of a week.
the peak load energy system C generates electrical energy from the chemical operating materials M61 during the peak load requirement during the working days, which can then be fed into an energy network at a correspondingly high price.
the need for chemical supplies M61 significantly exceeds the production output P g of the recycling plant A, which is marked with (-). This above-average consumption is taken from the BA operating fluid store.
the demand drops sharply and the production output P g exceeds the demand P e , which is marked with (+).
the fuel supply BA is refilled.
the energy system C can be shut down to a minimum power level, as in Figure 7 (d) shown, or the energy unit C is completely decommissioned, so that the base load P c is completely covered by the base load energy unit AF.
a device therefore has the essential advantage that only a part P f of the constant effective power P d is obtained in the form of thermal power, which must be immediately converted into electrical and / or mechanical energy, as in a conventional power plant.
This part P f can be used to deliver the power for the base load base P c .
Another part P g of the effective power P d is temporarily stored in the memory BA in the form of operating materials M61.
the demand (P e - P f ) which exceeds the thermal power of the base load energy unit AF can then be met by the peak load energy system C from the operating fluid storage BA.
a device Z according to the invention can be designed with a significantly smaller installed thermal output in order to be able to cover a specific requirement profile, for example 75% or 50% of the thermal output of a comparable conventional power plant. This leads to significantly lower investment costs.
a device according to the invention can be designed and optimized such that the power P f generated directly from thermal energy is reduced in favor of the power P g generated from the operating materials M61.
Such a variant is in Figure 7 (c) shown.
Such a device according to the invention can cover a significantly higher amount of energy when covering a reduced base load base P c2 to save. The corresponding stored energy can finally be used to generate peak load power P e2 , which can then be sold at a higher price.
FIG. 8 A first possible variant of the construction of a plant A for the thermal-chemical utilization of carbon-containing solids with a method according to the invention or in a device according to the invention is shown in Figure 8 shown schematically.
the recycling system A of the device Z according to the invention comprises a recycling unit AB with three sub-units AC, AD, AE for carrying out the three process stages P1, P2, P3 of the method according to the invention, which are connected to form a closed circuit in such a way that they form a closed, cyclical gas stream allow.
the processing unit AH only the silo A91 for the preparation of the carbon-containing material M11 prepared for the process is shown. From the discharge unit AG, only the slag storage A92 is shown.
the recycling plant A may or may not comprise an energy unit (not shown). This is not relevant for the functionality of the recycling process.
the three subunits AC, AD, AE of the utilization unit AB are connected to form a closed circuit in such a way that they allow a closed, cyclical gas flow.
first process stage P1 pyrolysis stage
first subunit AC carbon-containing starting material M11 is pyrolyzed under pressure, resulting in pyrolysis coke M21 and pyrolysis gases M22.
second process stage P2 gasification stage
second subunit AD pyrolysis coke M21 is gasified to synthesis gas M24, which is finally in a third process stage P3 (synthesis stage) or the third subunit AE to hydrocarbons and / or solid, liquid , or gaseous products M60 is reacted.
the carbon-containing starting materials M11 to be processed are continuously fed into the circuit from a feed device AH, P6 via the first process stage P1.
the products M60, M61 generated from the synthesis gas M24 are continuously withdrawn from the third process stage P3.
the various residues M91, M92, M93 are continuously removed from the cycle.
a large number of carbon-containing materials can be used as the starting material M11 for a recycling process according to the invention, in particular waste, biomass, coal and other heterogeneous materials such as contaminated soil, but also already deposited waste, for example from landfills. This enables the environmentally friendly and cost-effective dismantling of open landfills.
Solid-liquid petroleum-containing materials that are difficult to use such as oil shale, oil sand, or oil sludge, can also be used in a method according to the invention.
Carbon-containing by-products of the chemical or petroleum industry can also be used as additives M12, which otherwise cannot be used any further and may even have to be flared.
the calorific value of the raw materials, the carbon content, water content, as well as the content of non-combustible residues such as metal, glass and ceramics can vary widely.
the starting material can be shredded to a piece size suitable for a particular recycling plant, the preferred piece size being derived from the consistency of the material and from the specific design of the first pressure reactor or the reactor-internal delivery system. For processing with a moving grate, for example, a piece size of approx. 5-10 cm is well suited.
the first process stage P1, AC comprises a first pressure reactor A13, in which pyrolysis of the carbon-containing starting material M11 takes place under pressure.
the starting material M11 is introduced into the pressurized pyrolysis reactor A13 via a suitable pressure lock A11.
the pyrolysis reactor A13 consists of a horizontal pressure body A14, in which the lumpy material is conveyed horizontally along the reactor during the pyrolysis by means of a schematically illustrated feed grate A15 with grate plates moved to and fro.
Any other conveyor device suitable for the continuous feed of the starting material to be processed can also be used, for example roller grates, chain conveyors, screw conveyors, etc.
a rotary kiln can also be used.
the material is continuously transported through the pressure reactor A13 at a temperature of approx. 300-800 ° C and a pressure of 1 to 60 bar and pyrolysed with the exclusion of oxygen.
the temperature is selected such that, in addition to maintaining the pyrolysis reaction, the desired operating pressure is maintained, on the one hand due to the expansion of the gases due to the temperature, and on the other hand due to the new production of pyrolysis gases.
a minimum temperature of 450 ° C ensures a constant reaction of free oxygen compounds during pyrolysis.
An operating temperature of 500-600 ° C and an operating pressure between 5 and 25 bar are particularly suitable.
Process steam M50 also serves to maintain the operating temperature of the first reactor.
An external heat supply such as a heat exchanger or an external heater can also be present. The latter is also advantageous when starting up the recycling plant A from the cold state.
Return gas M25 from the third process stage (synthesis stage) P3 is fed to the first pressure reactor A13 after passing through a compressor A42.
the return gas M25 mainly contains carbon dioxide, as well as water vapor and unreacted carbon monoxide and hydrogen in the synthesis stage, as well as residual contents of low molecular weight hydrocarbons.
additional carbon with a high calorific value can be introduced into the reactor A13, for example in the form of coal or heavy oil.
additives M12 can be added to the starting material M11 beforehand, or can be introduced separately into the reactor A13.
the mixing of viscous additives M12 with solid starting material M11 facilitates the conveyance of viscous material within the reactor. Liquid M12 additives also increase the amount of pyrolysis gas, and thus the operating pressure.
Pyrolysis coke M21 which consists essentially of solid carbon and inorganic residues, is produced during pyrolysis in the first process stage P1.
the pyrolysis coke M21 is discharged at the end of the pressure reactor A13.
the pyrolysis gases M22 produced during pyrolysis contain both gaseous and solid and liquid materials at room temperature. The composition of pyrolysis gases M22 naturally depends heavily on the starting materials and may also contain pollutants.
the pyrolysis coke M21 is conveyed under pressure into the pressure reactor A21 of the second process stage P2.
a closed screw conveyor for example, is again suitable.
a pressure lock can also be provided.
the pyrolysis gases M22 are also fed into the second pressure reactor A21 via a separate transport line.
a compressor A41 arranged in the transport line conveys the pyrolysis gases into the second pressure reactor A21, which is at a higher operating pressure.
the operating temperature is between 600 and 1600 ° C.
the solid carbon is gasified in pyrolysis coke M21, using carbon dioxide and optionally oxygen and / or water vapor as the gasifying agent, to carbon monoxide and hydrogen, according to reactions I, II and III.
the carbon dioxide comes primarily from the return gas M25. Additional M33 carbon dioxide can also be fed into the circuit.
the water vapor primarily consists of the residual moisture of the raw material M11. Process steam M50 can also be fed.
the thermal energy necessary for the course of these endothermic pyrolysis reactions comes, for example, from a partial oxidation of the solid carbon (reaction III) with oxygen M31 passed into the second pressure reactor A21.
the exothermic water gas shift reaction IV can also contribute to this.
the ratio between carbon monoxide and hydrogen which is important for the later synthesis in the third process stage P3 is given by the water gas shift reaction IV and can be influenced on the right-hand side by adding process steam M50. However, it is advantageous to add the total amount To keep water in the system as low as possible and instead introduce additional M32 hydrogen directly into the third process stage.
the second process stage likewise comprises a pressure body A22, in which the pyrolysis coke is conveyed within the reactor A21 by a feed grate A23.
a feed grate A23 in which the pyrolysis coke is conveyed within the reactor A21 by a feed grate A23.
other conveyor systems are also possible, as have already been discussed for the first pressure reactor A13. This has the advantage that the pyrolysis coke can be processed in the second process stage without further preparation.
the second reactor can also be designed differently.
the pyrolysis coke could be crushed or ground beforehand, which then enables gasification of the coke in an eddy current or entrained flow.
this variant has the disadvantage that the particles have a shorter retention time in the reactor, which requires a more homogeneous material feed and preparation.
such systems require more precise and faster control of gas flow speed and other process parameters.
the reactive surface of lumpy pyrolysis coke is comparatively small compared to a reaction in the eddy current, which is also possible, but this is compensated for by the comparatively long residence time in reactor A21 due to the high mass capacity of the pressure reactor.
Another advantage is the easier scalability. By simply extending the pressure reactor or a By enlarging the cross-section, the capacity and thus the turnover can be increased without the relevant process parameters such as pressure or temperature having to change. However, reactors with flight or eddy current cannot be scaled up easily and easily.
the oxygen M31 necessary for the partial oxidation and optionally the process steam M50 are blown into the ember bed formed by the pyrolysis coke, whereby the necessary thermal energy is generated and the reactor A21 is kept at operating temperature.
air could also be used, but the inert atmospheric nitrogen inflates the gas material stream circulating within the recovery unit and is difficult to remove. This significantly reduces the efficiency of the system, so that pure oxygen is always preferable.
the absence of nitrogen in the system also prevents the formation of nitrogen oxides.
the pyrolysis gases M22 are in Figure 8 Embodiment of a recycling plant A shown is blown into the gas phase above the ember bed in the pressure reactor A21, where the polyatomic molecules contained in the pyrolysis gases M22 are cracked and disassembled very quickly at the prevailing high temperatures.
the synthesis gas M24 formed in the second process stage therefore essentially no longer contains any organic molecules and can be used for the Fischer-Tropsch synthesis in the third process stage. Pollutants such as dioxin are also broken down.
the oxygen supply M31 into the ember bed and the point of entry of the pyrolysis gases M22 into the pressure reactor are advantageously chosen so that no dioxins can form, which can be achieved by a suitable spatial separation. Likewise, no oxygen should be present in the synthesis gas emerging.
unproblematic raw materials such as wood chips or straw or other unpolluted biomass
residues M91 remain in the form of ash and inert residues as well as possibly unprocessed carbon. If slagging is desired, additives can be added that lower the ash melting point. For this purpose, lime powder can be added to the starting material M11, for example.
the slag is removed from the second pressure reactor A21 via a suitable pressure lock A28 from the pressure area of the recycling plant AB.
the second process stage can alternatively be designed so that unreacted pyrolysis coke is conveyed to the beginning again at the end of the pressure reactor and can thus run through the reactor a second time. This enables a shorter design of the pressure reactor.
the synthesis gas stream M24 is discharged from the second pressure reactor A21, and a main part M24a is passed through a suitable heat exchanger A44, where the gas stream producing process steam M50 for in-process purposes and / or steam M52 for energy generation in an energy unit AF (not shown) is cooled to a temperature which is suitable for the Fischer-Tropsch synthesis in the third process stage P3. Due to the lower temperatures, the pressure drops and the equilibrium of reactions I, II and IV shifts, as a result of which the proportion of carbon dioxide in the synthesis gas increases again. Solid carbon M94 can also separate from the gas stream in the form of graphite. The carbon M94 can be used as the starting material M11, M12 be recycled, otherwise used as a valuable material, or removed from the system as residual material.
the synthesis gas stream M24a is then fed to a cyclone A47, where dust M92, mainly consisting of residual coke and ash, is separated off.
the residual dust M92 can be returned to the first pressure reactor A13 or the second pressure reactor A21, or it is processed and / or disposed of.
a cyclone another suitable gas flow cleaning device can also be used.
the carbon M94 arrives with the synthesis gas stream in the Fischer-Tropsch reactor A31, where it can be removed or filtered off together with the carbon formed as a by-product in the Fischer-Tropsch reaction.
the synthesis gas M24 is then fed via a pressure regulator A48 to a third pressure reactor A31 of the third process stage P3, in which a Fischer-Tropsch synthesis is carried out.
Pressure regulation A48 reduces the pressure to the value desired for the third process stage.
additional hydrogen M32 can be fed into the Fischer-Tropsch reactor A31.
the necessary solid-state catalysts M37 are also supplied.
Suitable for the synthesis stage are, for example, low-temperature Fischer-Tropsch processes, which are operated, for example, at 210 to 250 ° C. and, above all, deliver diesel-like products and long-chain components in the form of waxes. The latter can then be used for example by hydrocracking.
High-temperature processes with temperatures between 320 and 350 ° C in turn supply considerable amounts of methane, short-chain alkanes and alkenes, as well as higher amounts of light petrol.
tube-bundle reactors are suitable, in which the synthesis gas flows from top to bottom through cooled tubes filled with catalyst. Return gas and products leave the tube at the bottom.
the steam M51, M50 obtained by the cooling device A32 contains considerable thermal energy, but is not yet hot enough for efficient utilization, for example in a steam turbine of an energy unit AF. It is therefore used advantageously for hot steam generation M52, for example in the heat exchanger A44, in order to increase the overall energy efficiency of the system.
the interaction of a recycling unit AB and a further energy-generating unit AF of a recycling system A is already shown in FIGS Figures 3 to 5 been received.
the gas stream M25 which leaves the Fischer-Tropsch reactor A31, contains, in addition to unreacted carbon monoxide and hydrogen gas, water vapor, carbon dioxide and gaseous reaction products M60.
a portion of volatile M60 hydrocarbons can be condensed out, for example, using a cooling column (not shown).
Water M41 can also be condensed out and thus removed from the return gas and thus from the material flow.
Part M25b can be separated as a process product from the remaining return gas stream.
the remaining return gas stream M25a is compressed in a compressor A42 and fed back into the first reactor A13.
the cyclical conveying of the gas flow within the recycling plant A takes place primarily due to the prevailing pressure differentials along the circuit. These are primarily generated by the two compressors A41, A42. Depending on the design of the system, one of the two compressors can be omitted, which lowers the overall cost of the system. If the plant contains only one compressor (as for example in the second exemplary embodiment of a recycling plant in Figure 9 ), the arrangement in front of the first reactor A13 has the advantage that the corresponding compressor A42 has to compress a smaller gas volume than a compressor A41 between the first and second process stages, where the pyrolysis gases are added and the total volume is larger due to the higher temperature , or even between the second and third process stages.
compressor A41 If the compressor A41 is dispensed with, there is only a slight pressure drop between the two reactors A13, A21, so that the first and second process stages run essentially at the same pressure. The gas flow then runs from compressor A42 via first A13, second A21 and third reactor A31 back to compressor A42. If, on the other hand, the compressor A42 is dispensed with, the pressure within the third reactor A31 and first reactor A13 is essentially the same.
a compressor can also be arranged between the second and third process stages. For reasons of entropy, at least one compressor or other funding must be available to promote the gas flow and to keep the process going.
pressure accumulators can be provided along the gas circuit M22, M24, M25 (not shown). Similarly, it is also possible to provide a buffer for the M21 pyrolysis coke.
the compressor A41 can produce a pressure difference of several bar with reasonable energy expenditure.
the first process stage could then be operated at a significantly lower pressure than the second process stage.
the first process stage can even be carried out under normal pressure or even under pressure.
FIG. 8 A possible method for starting up a recycling plant A as in is now discussed below Figure 8 shown.
the circuit and the three process stages are flushed and filled with an oxygen-free gas, advantageously with carbon dioxide and / or carbon monoxide and / or hydrogen gas or mixtures thereof, that is to say synthesis gas.
the second pressure reactor A21 which was previously filled with coke, is then heated, for example with gas burners.
the second reactor is separated from the circuit by closing the corresponding connections.
the conveyance A23 of the coke within the pressure reactor A21 is not yet switched on.
a temporary short circuit between the heat exchanger A44 and the pressure reactor A21 can be provided in the circuit (not shown) in order to circulate the heated gas in the system and to be able to heat the entire system section evenly.
the pressure is also increased to the setpoint.
the first pressure reactor A13 which was also previously filled with coke, is separated from the circuit and heated to the intended operating temperature of the first process stage.
the pressure is also brought to the desired value for the first process stage.
Material delivery A15 in the first reactor remains switched off.
heating should preferably take place without starting material, since pyrolysis of the starting material below a minimum safe operating temperature of 450 ° C. can lead to the formation of explosive mixtures.
the coke on the other hand, has already been pyrolyzed and only serves to supply coke to the second process stage when the cycle is started later.
the Fischer-Tropsch reactor A31 is also separated from the circuit and brought up to operating conditions. After the operating conditions in the various process stages of the recycling plant have been reached, the various conveyor systems A15, A23 are started up slowly, the circuit is opened, and the compressors A41, A42 are put into operation, so that the recycling plant AB finally comes to a state of equilibrium with the desired operating parameters.
FIG Figure 9 Another embodiment of a utilization unit AB of a device Z according to the invention is shown in FIG Figure 9 shown. For the sake of clarity, the boundary of the recycling unit AB has not been shown.
the branched synthesis gas stream M24b is not fed directly back into the first reactor A13, but instead is led through a heating device A16 of the pressure reactor A13 and then combined again with the synthesis gas M24a.
a further heating device A17 can be provided, which is operated with process steam M50.
a heat exchanger A45 is arranged in the return gas stream M25a and serves to heat the return gas stream M25a by process steam M50.
the return gas stream also serves to supply heat to the first pressure reactor A13.
no pressure reduction is provided before the third pressure reactor A31.
the pressure control in the third process stage takes place directly via the pressure control in the second process stage and the subsequent pressure drop due to the cooling of the synthesis gas stream M24 in the heat exchanger A44, as well as the compressor A42.
the low-temperature Fischer-Tropsch reactor of the third process stage is replaced by a high-temperature Fischer-Tropsch reactor in which the catalyst is present as a swirling dust.
the gaseous, short-chain hydrocarbons which are preferably formed in the high-temperature Fischer-Tropsch synthesis and remain in the return gas after a first condensation stage are separated from the smaller molecules of the return gas, such as carbon dioxide, carbon monoxide and hydrogen, by means of permeation gas filters.
Such systems are known for example from the petrochemical industry for the purification of natural gas. In the present case, they serve to generate a first, hydrocarbon-rich gas phase and a second, low-hydrocarbon gas phase.
the hydrocarbon-rich gas phase is further used as fuel for a second generator stage to generate electrical energy, or is processed into liquid gas and natural gas.
the low-carbon and carbon dioxide-rich second gas phase is sent back into the circuit as return gas.
the third process stage P3 contains a liquid-phase methanol synthesis reactor instead of a Fischer-Tropsch reactor.
the liquid phase methanol synthesis known from the prior art is particularly suitable for producing methanol in high yield from synthesis gas with a higher proportion of carbon dioxide.
the synthesis takes place in a "slurry bubble column reactor" in which the synthesis gas is blown into a slurry of the powdery catalyst in an inert mineral oil.
the reaction is highly exothermic, so a cooling device is necessary.
the gaseous methanol produced leaves the pressure reactor together with unreacted synthesis gas. After the entrained mineral oil and catalyst have been separated off, the methanol is condensed out.
Methanol is a valuable basic product for the chemical industry and can also be used as a fuel. Methanol can also be used as an additive to gasoline, for example in Germany a proportion of up to 3% methanol in vehicle gasoline is permitted. The methanol can also be used in particular as operating medium M60 for a second generator stage.
the method according to the invention shown is based on a cyclic material flow through the three process stages P1, P2, P3 of the utilization unit AB, carbon-containing Starting material M11 is fed into the circuit as a carbon supplier and energy source and the products of the synthesis stage are branched off as valuable materials M60 or as operating materials M61 for the energy system C of the device according to the invention.
the slag M91 and other residual materials M92, M93, M94, and water vapor in the return gas M25 are continuously removed from the circuit.
the steam produced in the heat exchangers is used on the one hand as process steam M50 for the operation of the system, thus increasing the efficiency and effectiveness of the system.
the hot steam M51, M52 can be used for energy production in an energy unit AF.
an energy-rich product M60, M61 namely the different fractions of the Fischer-Tropsch stage, is produced from an energy-rich but heterogeneous and difficult-to-use solid starting material M11. These can then be used further, for example as liquid fuels or as educts for the chemical industry.
the energy required for the operation of the recycling plant AB comes from the partial oxidation reaction in the second process stage, with an excess of the chemical energy generated there (in the form of the synthesis gas) later in the exothermic Fischer-Tropsch reaction of the third process stage again in thermal energy Form of steam M50, M51 is converted.
superheated steam M52 is generated from the carbon-containing starting material M11 for continuous operation of a base load energy unit AF, and fuel M61 for flexible operation of a peak load energy unit C.
the pressure and temperature in the third reactor A31 are the decisive parameters for the production of the hydrocarbons and other products in the third Fischer-Tropsch stage P3.
the pressure can be checked briefly with the A42 compressor by increasing or decreasing its output.
the temperature can in turn be controlled by the cooling capacity of the A32 heat exchanger.
the pressure can be controlled via the pressure in the synthesis gas stream M24, on the one hand by changing the operating pressure and the temperature in the second process stage, and on the other hand by controlling the cooling capacity of the heat exchanger A44, and thus the temperature and pressure drop in the synthesis gas stream M24.
the control of a recycling plant A is comparatively simple, since the plant runs in an equilibrium state with feedback, and to control a few less relevant parameters, a plurality of parameters, the individual operating parameters of the various plant components, which can affect the balance slowly or quickly, can be changed.
the recycling method according to the invention is preferably carried out with an increased carbon dioxide content. Among other things, this shifts the reaction equilibrium IV to the left (more carbon monoxide). Such an increased carbon dioxide content is made possible with the highest possible absolute amounts of carbon monoxide and thus processing power increased operating pressure of the treatment plant between 10 and 60 bar. Higher or lower pressures are also possible, but less efficient.
the recycling plant can be optimized with regard to various aspects. For example, if carbon dioxide-neutral biomass, such as wood chips, is to be used in the third process stage to produce valuable materials such as diesel and gasoline-analogous hydrocarbons and waxes, etc., the process is based on the best possible relationship between the costs for the biomass and the current ones Operation and the value of the recyclables produced. However, less attention needs to be paid to the emission of carbon dioxide, since it is carbon dioxide-neutral biomass. In order to further improve the ecological balance, the external energy supply (electrical power etc.) can be reduced, with possibly increased biomass consumption.
the external energy supply electrical power etc.
the system is operated in such a way that as little carbon dioxide as possible has to be removed from the cycle and released into the environment. This may then lead to an increased need for external energy.
the recycling plant can also be optimized for maximum throughput of starting material, so that possibly unprocessed pyrolysis coke leaves the third process stage together with the slag.
the pyrolysis coke which is not problematic from an environmental point of view, can then be deposited together with the slag.
Such a variant is advantageous, for example, if large amounts of contaminated material are to be rendered harmless in a carbon dioxide-neutral manner.
the operating temperature of the second process stage P2 can also be optimized.
the operating temperature of the second process stage P1 of the processing unit AB can be reduced in order to increase the throughput in the second reactor A21. This may then result in certain volatile substances in the pyrolysis gas M22 no longer being cracked and in the synthesis gas M24 entering the Fischer-Tropsch reactor A31.
benzene from the starting material such as heavy oil, can reach the Fischer-Tropsch synthesis products in smaller quantities. These materials remain there as part of a liquid M61 fluid, but can also be separated if necessary.
FIG 10 schematically shows an advantageous embodiment of a recycling unit AB.
a heat exchanger A46 is arranged, which serves to heat the pyrolysis gases M22 to the operating temperature of the second process stage with process steam M50 before entering the second pressure reactor A21. It is also possible to charge the A46 heat exchanger with hot M24 synthesis gas.
the compressor A43 is arranged in the transport line of the synthesis gas M24, after a heat exchanger A44. Although the mass flow is greatest at this point in the system, the gas volume to be managed for the compressor A43 is smaller due to the greatly reduced temperature after the heat exchanger A44, and the operating temperature for the compressor is more favorable because it is lower.
FIG Figure 11 A further advantageous embodiment of a utilization unit AB of a device Z according to the invention is shown in FIG Figure 11 shown, which is particularly suitable for the production of liquid fuels M61 from unpolluted biomass such as wood chips.
the pyrolysis gases M22 are not passed into the second process stage P2 but into the third process stage P3, the synthesis gas M24 not into the third process stage P3 but into the first process stage P1, and the return gas M25 not into the first process stage P1 but into the second process stage P2.
the hot synthesis gas stream M24 heats the pyrolysis material and maintains the operating temperature.
the pyrolysis gas stream M22 emerging from the first process stage then contains, in addition to the actual pyrolysis gases, also the synthesis gas fraction from the second process stage, which therefore makes a loop over the first process stage.
the synthesis gas component in the pyrolysis gases M22 is reacted, while those pyrolysis gas components which do not already condense in the heat exchanger A45 M23 dissolve in the liquid phase of the synthesis reactor A31. Since the purity requirements are not particularly great when the products M60 of the third process stage are used directly as fuel or as operating material for the second drive device C11, cracking of the pyrolysis gases can be dispensed with.
the fuel or operating fluid M61 is then cleaned to remove unsuitable residues such as organic acids etc.
the condensed portions M23 of the pyrolysis gas which have a low melting point and boiling point and contain a significant portion of tar, can advantageously be fed to the second process stage as a solid or liquid additive M23.
the return gas stream M25 is then compressed A42, heated A46 and introduced into the second process stage P2, so that a cycle is formed again. Since it is not necessary to crack the gases introduced into the A21 pressure reactor, the second process stage can be operated at a lower operating temperature.
Figure 12 shows an embodiment of a utilization unit AB, in which the first and second process stages P1, P2 are carried out in a common pressure reactor A24.
the pyrolysis takes place in a first chamber A25 of the reactor A24, the gasification in a second chamber A26.
the two chambers A25, A26 are formed by a partition A27 arranged in the pressure reactor A24, with a passage through which a common conveyor system conveys the pyrolysis coke M21 and the pyrolysis gas M22 flows.
the partition A27 serves primarily to thermally insulate the two chambers A27, A26, so that different operating temperatures can be reached in the two process stages. It is also possible to equip such a common pressure reactor with more than two separate chambers.
water M40 can be used as an additional expansion means in an advantageous variant of such a drive device.
a certain amount of water is injected into the cylinder after the ignition of the combustion process, for example after the compressed fuel-air mixture has auto-ignited in a diesel engine.
This water which is preferably finely atomized, is then evaporated by the thermal energy of the exothermic oxidation reaction.
the resulting increase in gas pressure or gas volume due to the water vapor thus contributes to the generation of the kinetic energy, however at the same time the temperature of the total mixture of combustion gases and water vapor drops.
this is unproblematic or even desirable because the higher energy density of a reaction with pure oxygen results in significantly higher reaction temperatures, which improves the thermodynamic efficiency but can also put more stress on the parts of the drive device C11.
the water can also be introduced as M50 steam.
a certain proportion of liquid water can also be mixed with the liquid fuel.
superheated steam also acts as an additional oxidizing agent in addition to oxygen.
drive devices C11 for a peak load energy system C of a device Z is described and explained in more detail, using the example of an internal combustion engine in the form of a piston engine with a cylinder.
drive devices C11 designed as internal combustion engines can also be designed as turbines or Wankel motors, etc.
the hot combustion gases are used in accordance with the functional principle of the respective type of internal combustion engine for the performance of mechanical work, for example for operating a generator system, and are partially relaxed.
the M27 oxidizing gas then leaves the combustion chamber.
a drive device C11 as a heat engine with external combustion, for example as a steam engine or steam turbine.
the internal combustion engine C11 shown has a cylinder C22 and a piston C23 movably arranged therein, which together form a closed combustion chamber C21.
a feed device C27 shown only schematically oxygen M31 is introduced into the expanding combustion chamber C21 in a first cycle.
the oxygen M31 is then compressed in a second cycle, and at the end of the second cycle, the operating medium M61 is introduced into the combustion chamber C21 and burned using a feed device C29.
the expanding combustion gases M27 perform mechanical work
the partially relaxed combustion gases M27 are removed from the combustion chamber C21 by a ventilation device C24 (not shown in more detail).
the hot oxidation gases M27 which essentially consist only of carbon dioxide and water vapor, are then cooled in a downstream heat exchanger C12. This reduces the volume of these M27 oxidizing gases. As a result of the cooling, most of the water M41 condenses out and is separated off.
the remaining residual gas M26 which essentially only consists of carbon dioxide and possibly residual carbon monoxide and unreacted operating materials, is compressed in a compressor C13 arranged in series and collected in a pressure accumulator BB.
the condensation stage C12 before compression reduces the undesirable formation of condensate droplets in the compressor C13.
the illustrated internal combustion engine C11 has no emissions. Since the device is not operated with air or similar gas mixtures as the oxidizing agent, no air-specific pollutants such as nitrogen oxides can arise. The water generated during the combustion is unproblematic and can be separated. The carbon dioxide is in as residual gas M26 managed the cycle of the recycling plant AB. Unburned parts of the fuel either condense out together with the water and are separated off, or are compressed together with the carbon dioxide. The oxidation gases M27 from the drive device C11 can also be passed directly into the first or second process stage without cooling.
peak load energy unit C is spatially separated from the recycling plant A, and if direct return of the residual gases M26 is not practical, then these can also be compressed to a very high degree and transported back from the energy plant C to the recycling plant A under high pressure in pressure accumulators BB.
FIG Figure 14 A further possible embodiment of a drive device C11 configured as an internal combustion engine is shown schematically in FIG Figure 14 shown.
water M40 is introduced into the combustion chamber C21 by means of a feed device C28 which is only shown schematically. This is preferably done in such a way that a certain amount of water, liquid or vapor, is injected into the combustion chamber C21 and finely distributed during or after the combustion reaction. This water is heated by the heat of combustion, whereby the total gas volume in the combustion chamber C21 increases, and thus also the gas pressure or gas volume available for the performance of the mechanical work. Accordingly, the amount of fuel can be reduced while maintaining the same performance.
water M40 can also be introduced into the oxidizing gas stream M27 when it has left the combustion chamber C21.
Such a variant has the advantage that the combustion reaction in the combustion chamber can proceed efficiently at the highest possible temperatures, and at the same time the resulting temperature of the oxidizing gas stream is so low that the subsequent devices C12, C13 are subjected to less stress.
the amount of water and the time of injection are coordinated with the supply of fuel M61 and oxygen M31 so that the combustion reaction can take place efficiently.
the resulting temperature during the oxidation reaction is advantageously essentially such that the thermodynamic efficiency of the heat engine is as high as possible.
the oxidation gases M27 are first compressed in a compressor C13 before they are subsequently cooled in the heat exchanger C12.
This variant is also made with the internal combustion engine C11 without water injection Figure 13 can be combined, and vice versa, and can be used generally for a drive device C11.
the energy necessary for the operation of the compressor of a drive device C11 is advantageously generated by the drive device itself.
the achievable efficiency of the drive device decreases, but at the same time the emission-free nature of the drive device mentioned is achieved.
the achievable power is greater with the same motor dimensions, which compensates for the loss of power.
the compressor can be operated directly with the crankshaft of a piston-type internal combustion engine, for example, via a suitable transmission.
the compressor can sit directly on the same shaft.
the oxidizing gases can then be condensed directly after the expansion process and the remaining stream can be compressed.
the oxidation gases are already precompressed after the combustion in the third cycle within the combustion chamber and are only then released by the venting device C24. If necessary, the downstream compressor C13 can also be omitted.
Such an embodiment is also possible as a two-stroke variant, because the new loading of the combustion chamber with the reaction mixture (fuel M61, oxygen M31, water M40) can take place very quickly in a drive device.
the combustion gases are pre-compressed and released from the combustion chamber towards the end of the stroke.
the gaseous oxygen can be blown into the combustion chamber under high pressure at the end of the upward stroke, since comparatively little oxygen is required for a complete combustion reaction, and water is available as an additional expansion agent.
the liquid operating fluid M61 and the water M40 as expansion medium can be injected into the combustion chamber C21 very quickly and under high pressure.
the energy consumption for the compressor C13 can be optimized by a suitable combination with one or more heat exchangers or cooling elements, in which the gas volume can be reduced by releasing thermal energy of the reaction gases to an internal or external heat sink.
the heat exchanger / condenser C12 can be used to generate steam, which can either be used to increase the efficiency of an energy unit AF of the recycling system, or to obtain process steam M50 for operating the recycling unit AB of the recycling system.
Figure 15 shows a particularly advantageous embodiment of a peak load energy system C, with a drive device C11, which is designed as a combined gas / steam turbine.
a drive device C11 which is designed as a combined gas / steam turbine.
fuel M61 is burned with oxygen M31 in a burner C25, forming a very hot combustion gas.
Water is introduced into the combustion chamber C21, preferably as superheated liquid water with a temperature of, for example, 250 ° C. and a pressure of 50 bar. The resulting water vapor mixes with the combustion exhaust gases, so that a hot (e.g.
oxidation gas M27a with a high proportion of superheated water vapor is produced, which emerges from the combustion chamber C21 and is converted into mechanical work in a subsequent turbine device C30, with which again a generator device C31 is driven.
the gas mixture in the combustion chamber behaves isochorically, so that the gas pressure rises, or isobarically, so that the gas volume increases accordingly, or both the volume and the pressure rise.
the subsequent turbine device C30 must also be designed accordingly. Suitable turbines C30 are known from the prior art and usually have several process stages. In an alternative variant, after a high pressure stage of the turbine device C30, partially released process steam M50 can be drawn off and used in another way.
the relaxed oxidizing gas M27b is passed into a condenser / economizer C12, where the water M41 is condensed out and separated off.
the remaining residual gas M26 which essentially contains carbon dioxide, is compressed in a compressor C13 and conveyed into the first process stage P1 of a recycling plant AB.
the compressor C13 is advantageously driven directly by the turbine C30.
the water M40 can also be mixed with the oxidizing gas stream M27a only after the combustion chamber C21, for example by means of a Venturi nozzle.
the amount of water M40 and the amount of fuel mixture M61, M31 and the other selectable parameters are advantageously matched to one another in such a way that the subsequent turbine achieves the highest possible energy utilization.
the proportion of water in the oxidizing gas mixture M27b should be as high as possible.
the highest possible pressure drop of the gas mixture on the condenser C12 is achieved, which increases the total pressure difference across the turbine C30, and thus its efficiency.
less residual gas M26 remains, which has to be compressed C13.
Another advantage of introducing steam into the combustion chamber is the cooling effect of the M50 steam.
the exothermic oxidation of the fuel mixture M61, M31 can lead to very high temperatures, up to 1000 ° C or even 2000 ° C. Such temperatures would place a great strain on the structures of the combustion chamber C21 and the subsequent turbine device C30.
the comparatively cold water vapor is preferably introduced into the chamber in such a way that it shields the walls of the combustion chamber C21 from the very hot flame C26.
the steam finally cools the entire gas mixture to 600 ° C to 800 ° C, which lowers the thermal load on the turbine blades and increases the service life accordingly.
the drive device shown also differs from a conventional gas turbine, for example, in that no compressor is connected upstream of the combustion chamber.
This allows the combustion chamber C21 to be designed much more simply than in the case of a gas turbine. Since the operating materials M61 are burned with pure oxygen M31, the achievable energy density is higher than when using air with its reduced oxygen content. In order to nevertheless increase the amount of oxygen that can be introduced into the combustion chamber C21 per unit of time, this can be pressurized in advance.
the turbine device C30 can be designed like a steam turbine, since the temperature and pressure ranges of the oxidizing gas M27a are essentially the same.
the drive device C11 of the energy system C remains idle. A small amount of steam keeps the C30 turbine moving while the generator device is not producing electricity. If the current requirement increases briefly, fuel mixture M31, M61 is injected into the combustion chamber C21 and ignited with an ignition device (not shown). At the same time, the amount of water M40, M50 injected is increased. The turbine C30 now starts up and the generator C31 is started up.
the drive device C11 can also be in continuous operation, for example at 10% to 50% of the output of the base load generator system AF. When the power requirement is increased, the system C can then be brought to maximum output in the shortest possible time, for example 500% of the output of the base load generator system AF.
a device Z according to the invention can thus adapt the overall performance very dynamically over a wide range.
a peak load energy unit C can also have a plurality of combustion chambers C21 and / or turbine devices C30.
the individual system parts are dimensioned and designed such that they can be efficiently broken down into individual modules, which are transported by truck and then reassembled can.
a maximum dimensioning of the modules, which allows transport without special means of transport, is particularly advantageous.
Such a modular device according to the invention has the advantage that it can also be created only temporarily, for example for an operating time of only a few years or even only months. As soon as there is no longer any need, it can be dismantled and reassembled at a new location.
Such a facility is particularly useful in mining, for example, if a larger energy infrastructure has to be built in a short time in remote mining areas, which is no longer required after the end of the mining activities.
a recycling system of a device according to the invention can be used to produce diesel fuel for vehicles and power generators of a remote open-cast mine from locally grown biomass and carbon-containing waste materials, and / or electrical energy for the operation of the infrastructure.
the reactors of the first and second process stages can be built as horizontal reactors with a comparatively small cross-section without reducing the throughput.
the reactor is simply lengthened accordingly in the longitudinal direction.
the reactor can then be assembled in the longitudinal direction from several modules flanged together.
the synthesis reactor can be scaled by using several reactors working in parallel.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Organic Chemistry (AREA)
Oil, Petroleum & Natural Gas (AREA)
Combustion & Propulsion (AREA)
Mechanical Engineering (AREA)
General Engineering & Computer Science (AREA)
General Chemical & Material Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Engine Equipment That Uses Special Cycles (AREA)
Carbon And Carbon Compounds (AREA)
Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Hydrogen, Water And Hydrids (AREA)
Coke Industry (AREA)
Luminescent Compositions (AREA)
Processing Of Solid Wastes (AREA)

EP19190005.9A 2009-11-20 2010-11-19 Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions Withdrawn EP3594313A1 (fr)

Applications Claiming Priority (6)

Application Number	Priority Date	Filing Date	Title
EP09176684A EP2325288A1 (fr)	2009-11-20	2009-11-20	Procédé et installation de traitement thermochimique et d'évaluation de substances contenant du carbone
EP10151481.8A EP2348254B1 (fr)	2010-01-22	2010-01-22	Système de ravitaillement en carburant pour un engin mobile
EP10151473A EP2348253A1 (fr)	2010-01-22	2010-01-22	Procédé d'exécution d'un travail mécanique sans émission
EP10154449A EP2325287A1 (fr)	2009-11-20	2010-02-23	Centrale sans émission de production d'énergie mécanique et électrique
PCT/EP2010/067847 WO2011061299A1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions
EP10777041.4A EP2501786B1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions

Related Parent Applications (2)

Application Number	Title	Priority Date	Filing Date
PCT/EP2010/067847 Previously-Filed-Application WO2011061299A1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions
EP10777041.4A Division EP2501786B1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions

Publications (1)

Publication Number	Publication Date
EP3594313A1 true EP3594313A1 (fr)	2020-01-15

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ID=44059230

Family Applications (2)

Application Number	Title	Priority Date	Filing Date
EP19190005.9A Withdrawn EP3594313A1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions
EP10777041.4A Active EP2501786B1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions

Family Applications After (1)

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EP10777041.4A Active EP2501786B1 (fr)	2009-11-20	2010-11-19	Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions

Country Status (40)

Country	Link
US (3)	US10450520B2 (fr)
EP (2)	EP3594313A1 (fr)
JP (1)	JP5791054B2 (fr)
KR (1)	KR101824267B1 (fr)
CN (1)	CN102762697B (fr)
AP (1)	AP3292A (fr)
AR (1)	AR079079A1 (fr)
AU (1)	AU2010320871B2 (fr)
BR (1)	BR112012011891B1 (fr)
CA (1)	CA2780856C (fr)
CL (1)	CL2012001299A1 (fr)
CO (1)	CO6541590A2 (fr)
CY (1)	CY1122410T1 (fr)
DK (1)	DK2501786T3 (fr)
EA (1)	EA024594B9 (fr)
EC (1)	ECSP12011973A (fr)
ES (1)	ES2758543T3 (fr)
GE (1)	GEP20146206B (fr)
HN (1)	HN2012001100A (fr)
HR (1)	HRP20191988T1 (fr)
HU (1)	HUE047176T2 (fr)
IL (1)	IL219746A (fr)
LT (1)	LT2501786T (fr)
ME (1)	ME03549B (fr)
MX (1)	MX2012005713A (fr)
MY (1)	MY158603A (fr)
NI (1)	NI201200092A (fr)
NZ (1)	NZ600722A (fr)
PH (1)	PH12012500987A1 (fr)
PL (1)	PL2501786T3 (fr)
PT (1)	PT2501786T (fr)
RS (1)	RS59514B1 (fr)
SG (1)	SG10201407559RA (fr)
SI (1)	SI2501786T1 (fr)
SM (1)	SMT201900616T1 (fr)
TN (1)	TN2012000213A1 (fr)
TW (1)	TWI522454B (fr)
UY (1)	UY33038A (fr)
WO (1)	WO2011061299A1 (fr)
ZA (1)	ZA201204529B (fr)

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2010
- 2010-11-18 UY UY0001033038A patent/UY33038A/es not_active Application Discontinuation
- 2010-11-19 AU AU2010320871A patent/AU2010320871B2/en not_active Ceased
- 2010-11-19 ES ES10777041T patent/ES2758543T3/es active Active
- 2010-11-19 US US13/509,883 patent/US10450520B2/en not_active Expired - Fee Related
- 2010-11-19 MX MX2012005713A patent/MX2012005713A/es active IP Right Grant
- 2010-11-19 SG SG10201407559RA patent/SG10201407559RA/en unknown
- 2010-11-19 LT LT10777041T patent/LT2501786T/lt unknown
- 2010-11-19 HU HUE10777041A patent/HUE047176T2/hu unknown
- 2010-11-19 CN CN201080052571.XA patent/CN102762697B/zh not_active Expired - Fee Related
- 2010-11-19 PT PT107770414T patent/PT2501786T/pt unknown
- 2010-11-19 AP AP2012006319A patent/AP3292A/xx active
- 2010-11-19 SM SM20190616T patent/SMT201900616T1/it unknown
- 2010-11-19 EP EP19190005.9A patent/EP3594313A1/fr not_active Withdrawn
- 2010-11-19 PH PH1/2012/500987A patent/PH12012500987A1/en unknown
- 2010-11-19 MY MYPI2012002196A patent/MY158603A/en unknown
- 2010-11-19 EP EP10777041.4A patent/EP2501786B1/fr active Active
- 2010-11-19 ME MEP-2019-308A patent/ME03549B/fr unknown
- 2010-11-19 TW TW099139890A patent/TWI522454B/zh not_active IP Right Cessation
- 2010-11-19 DK DK10777041T patent/DK2501786T3/da active
- 2010-11-19 CA CA2780856A patent/CA2780856C/fr active Active
- 2010-11-19 EA EA201270637A patent/EA024594B9/ru unknown
- 2010-11-19 NZ NZ600722A patent/NZ600722A/en not_active IP Right Cessation
- 2010-11-19 KR KR1020127015840A patent/KR101824267B1/ko active IP Right Grant
- 2010-11-19 PL PL10777041T patent/PL2501786T3/pl unknown
- 2010-11-19 GE GEAP201012757A patent/GEP20146206B/en unknown
- 2010-11-19 RS RS20191418A patent/RS59514B1/sr unknown
- 2010-11-19 WO PCT/EP2010/067847 patent/WO2011061299A1/fr active Application Filing
- 2010-11-19 BR BR112012011891A patent/BR112012011891B1/pt not_active IP Right Cessation
- 2010-11-19 AR ARP100104282A patent/AR079079A1/es not_active Application Discontinuation
- 2010-11-19 SI SI201031947T patent/SI2501786T1/sl unknown
- 2010-11-19 JP JP2012539341A patent/JP5791054B2/ja not_active Expired - Fee Related
2012
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UY33038A (es)	2011-06-30
ZA201204529B (en)	2013-02-27
CA2780856C (fr)	2019-02-12
JP2013511585A (ja)	2013-04-04
WO2011061299A1 (fr)	2011-05-26
US20200002632A1 (en)	2020-01-02
LT2501786T (lt)	2019-11-25
PH12012500987A1 (en)	2017-05-12
HUE047176T2 (hu)	2020-04-28
AU2010320871B2 (en)	2017-04-06
PT2501786T (pt)	2019-11-12
BR112012011891B1 (pt)	2018-05-08
EA024594B9 (ru)	2017-01-30
JP5791054B2 (ja)	2015-10-07
US20210032553A1 (en)	2021-02-04
CL2012001299A1 (es)	2012-08-24
US10450520B2 (en)	2019-10-22
CA2780856A1 (fr)	2011-05-26
AP2012006319A0 (en)	2012-06-30
CO6541590A2 (es)	2012-10-16
RS59514B1 (sr)	2019-12-31
ME03549B (fr)	2020-07-20
MX2012005713A (es)	2012-10-10
NI201200092A (es)	2013-04-15
DK2501786T3 (da)	2019-11-11
HRP20191988T1 (hr)	2020-03-20
AU2010320871A1 (en)	2012-07-12
NZ600722A (en)	2014-08-29
SI2501786T1 (sl)	2020-03-31
ECSP12011973A (es)	2012-08-31
EP2501786A1 (fr)	2012-09-26
MY158603A (en)	2016-10-18
CY1122410T1 (el)	2021-01-27
GEP20146206B (en)	2014-12-10
IL219746A0 (en)	2012-07-31
SG10201407559RA (en)	2015-01-29
AP3292A (en)	2015-05-31
US10844302B2 (en)	2020-11-24
AR079079A1 (es)	2011-12-21
US20120238645A1 (en)	2012-09-20
EP2501786B1 (fr)	2019-08-07
ES2758543T3 (es)	2020-05-05
TN2012000213A1 (en)	2013-12-12
TW201124519A (en)	2011-07-16
HN2012001100A (es)	2015-04-06
KR20120112469A (ko)	2012-10-11
PL2501786T3 (pl)	2020-03-31
EA201270637A1 (ru)	2012-11-30
IL219746A (en)	2016-05-31
SMT201900616T1 (it)	2020-01-14
EA024594B1 (ru)	2016-10-31
BR112012011891A2 (pt)	2016-08-02
CN102762697A (zh)	2012-10-31
CN102762697B (zh)	2016-08-10
TWI522454B (zh)	2016-02-21
KR101824267B1 (ko)	2018-01-31

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DE112005000402T5 (de)	2008-06-12	Verfahren und Vorrichtung zur Wasserstoffproduktion
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DE102012105736A1 (de)	2014-01-02	Verfahren zur Speicherung von Elektroenergie
WO2013034130A2 (fr)	2013-03-14	Séquestration écologique de dioxyde de carbone/augmentation de la quantité de bioénergie pouvant être obtenue à partir d'une biomasse
EP2325287A1 (fr)	2011-05-25	Centrale sans émission de production d'énergie mécanique et électrique
DE102009049914B4 (de)	2011-12-22	Kohlekraftwerks-Kombiprozess mit integrierter Methanolherstellung
EP2526177B1 (fr)	2020-06-24	Dispositifs sans émission pour effectuer des travaux mécaniques
EP3081289B1 (fr)	2019-06-19	Procédé de combustion de matières premières hydrocarbonées (hc) solides, liquides ou gazeuses dans un moteur thermique, moteur thermique et système de production d'énergie à partir de matières hydrocarbonées (hc)
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DE102013219254A1 (de)	2015-03-26	Energetisch optimiertes Verfahren zur stofflichen Kohle-/Biomassenutzung

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